JP2012054431A - Pressure-sensitive adhesive sheet for semiconductor wafer protection - Google Patents

Pressure-sensitive adhesive sheet for semiconductor wafer protection Download PDF

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Publication number
JP2012054431A
JP2012054431A JP2010196252A JP2010196252A JP2012054431A JP 2012054431 A JP2012054431 A JP 2012054431A JP 2010196252 A JP2010196252 A JP 2010196252A JP 2010196252 A JP2010196252 A JP 2010196252A JP 2012054431 A JP2012054431 A JP 2012054431A
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adhesive sheet
pressure
sensitive adhesive
wafer
semiconductor wafer
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Tsuyoshi Habu
剛志 土生
Fumiteru Asai
文輝 浅井
智一 ▲高▼橋
Tomokazu Takahashi
Eiichi Imoto
栄一 井本
Yuta Shimazaki
雄太 島崎
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Nitto Denko Corp
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Nitto Denko Corp
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Priority to JP2010196252A priority Critical patent/JP2012054431A/en
Priority to TW100129625A priority patent/TW201213483A/en
Priority to KR1020110087348A priority patent/KR20120024472A/en
Priority to CN2011102641711A priority patent/CN102382582A/en
Priority to US13/223,629 priority patent/US8546958B2/en
Publication of JP2012054431A publication Critical patent/JP2012054431A/en
Pending legal-status Critical Current

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/67—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere
    • H01L21/67005—Apparatus not specifically provided for elsewhere
    • H01L21/67011—Apparatus for manufacture or treatment
    • H01L21/67132—Apparatus for placing on an insulating substrate, e.g. tape
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    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
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    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
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    • C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
    • C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
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    • C08G18/757—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing at least two isocyanate or isothiocyanate groups linked to the cycloaliphatic ring by means of an aliphatic group
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • C09J175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
    • C09J175/16—Polyurethanes having carbon-to-carbon unsaturated bonds having terminal carbon-to-carbon unsaturated bonds
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    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/10—Adhesives in the form of films or foils without carriers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/22—Plastics; Metallised plastics
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/67—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere
    • H01L21/683—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere for supporting or gripping
    • H01L21/6835—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere for supporting or gripping using temporarily an auxiliary support
    • H01L21/6836—Wafer tapes, e.g. grinding or dicing support tapes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2170/00—Compositions for adhesives
    • C08G2170/40—Compositions for pressure-sensitive adhesives
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
    • C09J2203/326—Applications of adhesives in processes or use of adhesives in the form of films or foils for bonding electronic components such as wafers, chips or semiconductors
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/10—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet
    • C09J2301/12—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers
    • C09J2301/124—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers the adhesive layer being present on both sides of the carrier, e.g. double-sided adhesive tape
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/10—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet
    • C09J2301/16—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the structure of the carrier layer
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
    • C09J2301/312—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier parameters being the characterizing feature
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2475/00—Presence of polyurethane
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2221/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof covered by H01L21/00
    • H01L2221/67—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere
    • H01L2221/683—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere for supporting or gripping
    • H01L2221/68304—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere for supporting or gripping using temporarily an auxiliary support
    • H01L2221/68327—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere for supporting or gripping using temporarily an auxiliary support used during dicing or grinding

Abstract

PROBLEM TO BE SOLVED: To provide a pressure-sensitive adhesive sheet for semiconductor wafer protection which achieves no curvature (warpage) of the semiconductor wafer, excellent followability to a pattern, no lifting from a pattern with age, improved stress dispersion during grinding, less wafer cracks of wafer edge chips, no delamination in removal and no residue of a sticker even when the semiconductor wafer is ground to create an ultra-thin wafer or a large-diameter wafer is ground.SOLUTION: The semiconductor wafer protection sheet bonded to a surface of the semiconductor wafer for protection is one layer protection sheet having one adhesive surface and no boundary face between a base material and a sticker. The protection sheet has a stress relaxation ratio of 40% and over at 10% elongation, a tape lifting width after 24 hours increased by 40% and under in comparison with the beginning when bonded to a stepped portion by 30 μm, a thickness of the pressure-sensitive adhesive sheet of 5 μm-1000 μm and adhesion forces on both faces different from each other.

Description

本発明は、半導体ウエハを極薄にまで研削した後もしくは、大口径ウエハの研削をした後で半導体ウエハの反りの少ない半導体ウエハ保護用粘着シートに関する。   The present invention relates to a pressure-sensitive adhesive sheet for protecting a semiconductor wafer with less warping of a semiconductor wafer after grinding the semiconductor wafer to an extremely thin thickness or after grinding a large-diameter wafer.

近年、各種電子機器の小型化やＩＣカードの普及によって、半導体ウエハ等の電子部品のさらなる薄型化が望まれている。このため、従来は厚さが３５０μｍ程度であった半導体ウエハを、厚さ３０μｍ以下程度まで薄くする必要が生じている。また、生産性を向上するために、ウエハのさらなる大口径化が検討されている。   In recent years, with the miniaturization of various electronic devices and the spread of IC cards, it has been desired to further reduce the thickness of electronic components such as semiconductor wafers. For this reason, it is necessary to reduce the thickness of a semiconductor wafer, which has conventionally been about 350 μm, to a thickness of about 30 μm or less. Further, in order to improve productivity, further increase in the diameter of the wafer is being studied.

通常、半導体ウエハの製造では、ウエハの表面に回路パターンを形成した後、所定の厚さになるまでウエハの裏面をグラインダー等で研削することが行われている。その際、ウエハの表面を保護する目的で、ウエハ表面に粘着シートを貼り合わせた上で裏面研削することが一般的に行われている。また、ウエハを薄型に加工した後は、ウエハ表面に粘着シートを貼り合わせた状態で、次工程に搬送することがある。   Usually, in the manufacture of a semiconductor wafer, after forming a circuit pattern on the surface of the wafer, the back surface of the wafer is ground with a grinder or the like until a predetermined thickness is achieved. At that time, in order to protect the surface of the wafer, it is generally performed that the back surface is ground after an adhesive sheet is bonded to the surface of the wafer. Moreover, after processing a wafer thinly, it may be conveyed to the next process in a state where an adhesive sheet is bonded to the wafer surface.

しかし、ウエハの表面を粘着シートで保護した状態で極薄まで裏面研削した場合、研削後のウエハに反りが生じやすい。反りの生じたウエハは搬送中や粘着シートの剥離中に割れる問題がある。これは、粘着シートを貼り合わせたウエハの裏面を研削することにより、ウエハの強度よりも粘着シートの残留応力が勝ると、残留応力を解消しようとする力によってウエハに反りが発生すると考えられる。   However, when the back surface is ground to an extremely thin state with the surface of the wafer protected by an adhesive sheet, the wafer after grinding tends to warp. There is a problem that a warped wafer breaks during conveyance or peeling of the adhesive sheet. This is considered that if the residual stress of the pressure-sensitive adhesive sheet is greater than the strength of the wafer by grinding the back surface of the wafer to which the pressure-sensitive adhesive sheet is bonded, the wafer is warped by a force for eliminating the residual stress.

この研削後のウエハの反りは、粘着シートに残る残留応力による影響が大きいと考えられる。この残留応力は基材及び粘着剤から構成される粘着シートでは基材への粘着剤の塗工あるいは基材と粘着剤層の貼り合わせの製造工程と粘着シートをウエハへ貼り付ける際の工程で主に発生し、残留応力が存在した粘着シートを貼り合わせたウエハを極薄に研削すると、ウエハの強度よりも粘着シートの残留応力が勝り、この残留応力を解消しようとする力によってウエハに反りが発生すると考えられる。また、それゆえ、この残留応力を低減させるために、粘着シートの構成にも種々改良が加えられ残留応力が発生しないような構成が提案されている。例えば特許文献１では、基材フィルムと粘着剤層とで構成された半導体ウエハ保護用粘着シートであって、基材フィルムの引張り弾性率が０．６ＧＰａであるものが提案されている。   It is considered that the warpage of the wafer after grinding is greatly influenced by the residual stress remaining in the adhesive sheet. In the case of an adhesive sheet composed of a base material and an adhesive, this residual stress is a process of applying the adhesive to the base material or bonding the base material and the adhesive layer and a process of attaching the adhesive sheet to the wafer. When a wafer with a pressure-sensitive adhesive sheet that occurs mainly and is bonded to a wafer is ground to an extremely thin thickness, the residual stress of the pressure-sensitive adhesive sheet is superior to the strength of the wafer, and the wafer is warped by a force that tries to eliminate this residual stress. Is considered to occur. Therefore, in order to reduce the residual stress, various improvements have been made to the configuration of the pressure-sensitive adhesive sheet so that a residual stress is not generated. For example, Patent Document 1 proposes an adhesive sheet for protecting a semiconductor wafer composed of a base film and an adhesive layer, wherein the base film has a tensile elastic modulus of 0.6 GPa.

また、特許文献２では、基材と、その上に形成された粘着剤層とからなる半導体ウエハ加工用粘着シートであって、粘着シートの引張り試験において伸度１０％における１分後の応力緩和率が４０％以上であるものが提案されている。   Moreover, in patent document 2, it is the adhesive sheet for semiconductor wafer processing which consists of a base material and the adhesive layer formed on it, Comprising: Stress relaxation after 1 minute in 10% elongation in the tension test of an adhesive sheet The thing whose rate is 40% or more is proposed.

一般に、半導体ウエハ表面に貼り合わされる粘着シートは基材層と粘着剤層の構成で形成されている。このような粘着シートは製造工程において、基材に粘着剤を直接塗工してセパレータと貼り合せるか、セパレータに粘着剤を塗工して基材と貼り合せて製造するが、その際に基材及びセパレータが弛まない様にある程度のテンションで張る必要があるため、貼り合わさる際には必ず応力が発生する。
基材は粘着シートが半導体ウェハをサポートして取り扱い性を向上させるために、そのサポート性を向上させることも目的として使用されている。
また、ウエハの表面に貼り合わせる際には貼り合わせ機を用いて、貼り合わせテーブルの上にウエハの表面が上になるようにウエハを載置し、その上に粘着シートを粘着剤層が下になった状態で、貼り合わせ方向に沿って弛まないように引っ張りながら供給する。こうして粘着シートの粘着剤層をウエハの表面と対向させ、圧着ロールなどの押圧手段により粘着シートの基材側から、貼り合わせ方向に沿って順次圧着し貼り合わせを行う。
このときも、粘着シートには粘着シートを貼り合わせ方向に沿って引っ張る力と、粘着シートをウエハに圧着する力がかかるため、粘着シートをウエハに貼り合わせるとこれらの力が残留応力となって粘着シートに残る。
事実、上記特許文献に記載されたような、これらの粘着シートの諸特性は、半導体ウエハを極薄にまで研削する際、もしくは、大口径ウエハを研削する際に、研削後のウエハの反りを抑制するものとして必ずしも最適なものではなく、このため、研削後のウエハの反りをよりいっそう抑制することのできる半導体ウエハ保護用粘着シートの提供が望まれていた。 In general, the pressure-sensitive adhesive sheet bonded to the surface of a semiconductor wafer is formed of a base material layer and a pressure-sensitive adhesive layer. Such a pressure-sensitive adhesive sheet is produced by directly applying a pressure-sensitive adhesive to a substrate and bonding it to a separator in the manufacturing process, or by applying a pressure-sensitive adhesive to a separator and bonding it to a substrate. Since it is necessary to stretch the material and the separator with a certain degree of tension so as not to loosen, a stress is always generated when the materials and the separator are bonded together.
The base material is also used for the purpose of improving the supportability in order that the adhesive sheet supports the semiconductor wafer and improves the handleability.
When bonding to the wafer surface, a bonding machine is used to place the wafer on the bonding table so that the wafer surface is on top, and the adhesive sheet is placed on top of the adhesive sheet. In this state, supply while pulling so as not to loosen along the bonding direction. In this way, the pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet is opposed to the surface of the wafer, and is sequentially pressed and bonded along the bonding direction from the base material side of the pressure-sensitive adhesive sheet by a pressing means such as a pressure-bonding roll.
At this time, since the adhesive sheet is subjected to a force for pulling the adhesive sheet along the bonding direction and a force for pressing the adhesive sheet to the wafer, these forces become residual stresses when the adhesive sheet is bonded to the wafer. It remains on the adhesive sheet.
In fact, the characteristics of these adhesive sheets, as described in the above-mentioned patent documents, show that when a semiconductor wafer is ground to an extremely thin thickness or when a large-diameter wafer is ground, the warpage of the wafer after grinding is reduced. Therefore, it is not always optimal as a suppressor, and for this reason, it has been desired to provide an adhesive sheet for protecting a semiconductor wafer that can further suppress the warpage of the wafer after grinding.

また、近年ウエハ研削厚の極薄化に伴い、研削時の応力によるウエハ割れやウエハエッジ部の欠けがないことも望まれており、研削後にはウエハから粘着シートを剥離しなければならなく、その時にはウエハ表面の回路パターンに粘着剤が残るようなことがなく、かつウエハ表面に粘着シートや半導体ウエハ等に由来する分子レベルの汚染がないことも望まれる。
加えて、ダイシング時におけるウエハの固定のために、基材を含む２層以上からなる粘着シートを使用したときには、これらの層が互いに異なる弾性率を有するために、その界面にて刃に係る力等が変化することによって、粘着剤層の微小な塊が刃や粘着シートに付着するいわゆるダマが発生する。そして、そのダマが付着した刃や粘着シートが次以降の工程において、ウエハや粘着シートに付着してそれらの切断を困難にしたり、ウエハ割れの原因となることもあった。
さらに粘着シートによる半導体ウエハ等の反りの発生や、水等による洗浄の際に半導体ウエハと粘着シートの間に水等が侵入することもあった。このため、粘着シートが応力緩和性を示すことと共に、ウエハ表面に設けた凹凸に十分に粘着シートの粘着剤層が追従でき、切断時の剪断力によっても粘着シートに浮きが発生しないようにすることが必要とされていた。 In addition, as the wafer grinding thickness has become extremely thin in recent years, it is also desired that there be no wafer cracking or chipping at the wafer edge due to stress during grinding, and the adhesive sheet must be peeled off from the wafer after grinding. In some cases, it is also desired that the adhesive does not remain on the circuit pattern on the wafer surface and that the wafer surface does not have molecular level contamination derived from an adhesive sheet, a semiconductor wafer or the like.
In addition, when a pressure-sensitive adhesive sheet comprising two or more layers including a substrate is used for fixing the wafer during dicing, these layers have different elastic moduli. And the like change, so-called lumps in which a fine lump of the pressure-sensitive adhesive layer adheres to the blade or the pressure-sensitive adhesive sheet are generated. Then, the blade and the adhesive sheet to which the lumps have adhered may adhere to the wafer and the adhesive sheet in the subsequent steps, making it difficult to cut them, or causing the wafer to crack.
Further, warpage of the semiconductor wafer or the like due to the adhesive sheet, or water or the like may enter between the semiconductor wafer and the adhesive sheet during cleaning with water or the like. For this reason, the pressure-sensitive adhesive sheet exhibits stress relaxation properties, and the pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet can sufficiently follow the unevenness provided on the wafer surface, so that the pressure-sensitive adhesive sheet does not float even by shearing force during cutting. It was needed.

特開２０００−２１２５２４号公報Japanese Patent Laid-Open No. 2000-212524 特開２０００−１５０４３２号公報JP 2000-150432 A

本発明は、半導体ウエハを極薄にまで研削する場合や、大口径ウエハの研削を行う場合であっても、半導体ウエハに反りを生じさせず、またパターンの追従性に優れ、経時によるパターンからの浮きがなく、研削時の応力分散性が良く、ウエハ割れ、ウエハエッジ欠けを抑制し、剥離時には層間剥離の発生がなく、ウエハ表面に粘着剤残渣が残らず、しかも切断時に粘着剤からなるいわゆるダマを発生させない半導体ウエハ用粘着シートを提供することを目的とする。   The present invention does not warp the semiconductor wafer even when grinding a semiconductor wafer to an extremely thin thickness or when grinding a large-diameter wafer, and has excellent pattern followability. So that it has good stress dispersibility during grinding, suppresses wafer cracking and wafer edge chipping, does not cause delamination during peeling, does not leave adhesive residue on the wafer surface, and is made of an adhesive during cutting It is an object of the present invention to provide a pressure-sensitive adhesive sheet for semiconductor wafers that does not generate lumps.

１．半導体ウエハ表面に貼り合わせる半導体ウエハ用粘着シートであって、前記粘着シートは、基材層が存在せずアクリルウレタン樹脂により形成された１層からなることを特徴とする半導体ウエハ用粘着シート。
２．前記粘着シートは１０％伸張時の応力緩和率が４０％以上であることを特徴とする１記載の半導体ウエハ用粘着シート。
３． 前記粘着シートを３０μｍの段差に貼付した時の２４ｈ後のテープ浮き幅は初期と比較して４０％以内の増加率であることを特徴とする１又は２記載の半導体ウエハ用粘着シート。
４．前記粘着シートの厚みが５μｍ〜１０００μｍであることを特徴とする１〜３に記載の半導体ウエハ用粘着シート。
５．前記粘着シートの両面の粘着力が互いに異なる１〜４記載の半導体ウエハ用粘着シート。 1. A pressure-sensitive adhesive sheet for a semiconductor wafer to be bonded to a surface of a semiconductor wafer, wherein the pressure-sensitive adhesive sheet is composed of one layer formed of an acrylic urethane resin without a base layer.
2. 2. The adhesive sheet for semiconductor wafer according to 1, wherein the adhesive sheet has a stress relaxation rate of 40% or more when stretched by 10%.
3. 3. The semiconductor wafer pressure-sensitive adhesive sheet according to claim 1 or 2, wherein the tape floating width after 24 hours when the pressure-sensitive adhesive sheet is attached to a step of 30 [mu] m is an increase rate within 40% compared to the initial stage.
4). The adhesive sheet for a semiconductor wafer according to 1 to 3, wherein the adhesive sheet has a thickness of 5 μm to 1000 μm.
5). The pressure-sensitive adhesive sheet for semiconductor wafer according to 1 to 4, wherein the pressure-sensitive adhesive strength on both sides of the pressure-sensitive adhesive sheet is different from each other.

（本発明の粘着シートの全体構成）
本発明は上記の構成を採用して、基材を有しないことによって、基材と粘着剤との界面が存在せず、1層になるように製造されてなる半導体ウエハ用粘着シートである。
ここで、基材を有しないことによって、基材層と粘着剤層との界面が存在せず、１層からなる粘着シートとは、上記背景技術に記載したような粘着剤層を担持するための基材フィルムを使用しない状態であるが、粘着剤層が基材以外の他の層、つまり基材として機能しない層と積層されることを排除するのではなく、粘着シート全体が残留応力を有しない程に薄い層の存在を許容することまでを包含する。
この粘着シートは応力緩和することができる粘着シートであるから、粘着テープの製造工程、シート貼り合わせ工程時に発生する残留応力も非常に小さくなる。このため、基材を有する粘着シートを使用したときとは異なり、このような粘着シートを用いて半導体ウエハの裏面研削を行うと、研削後のウエハの反りを低減することができる。 (Overall configuration of the pressure-sensitive adhesive sheet of the present invention)
The present invention is a pressure-sensitive adhesive sheet for a semiconductor wafer produced by employing the above-described configuration and having no base material, so that there is no interface between the base material and the pressure-sensitive adhesive, and it is a single layer.
Here, by not having a substrate, there is no interface between the substrate layer and the pressure-sensitive adhesive layer, and the single-layer pressure-sensitive adhesive sheet carries the pressure-sensitive adhesive layer as described in the background art above. However, it is not excluded that the pressure-sensitive adhesive layer is laminated with a layer other than the base material, that is, a layer that does not function as a base material. To allow the presence of a layer so thin that it does not have.
Since this pressure-sensitive adhesive sheet is a pressure-sensitive adhesive sheet that can relieve stress, the residual stress generated during the pressure-sensitive adhesive tape manufacturing process and the sheet bonding process is also very small. For this reason, unlike when an adhesive sheet having a substrate is used, if the backside grinding of the semiconductor wafer is performed using such an adhesive sheet, the warpage of the wafer after grinding can be reduced.

さらに、基材を有しない粘着シートを切断する際には、刃が切断する際に硬さ、伸び率等が異なる２層を切断しなくても良いので、刃は同じ力、及び同じ応力にて粘着シートの層方向に移動して粘着シートを切断することが可能になるので、２層のときのように層の界面にて刃に係る力等が変化することによる、粘着剤層の微小な塊が刃や粘着シートに付着するいわゆるダマの発生を防止することが可能となり、ダマが付着した刃や粘着シートが次以降の工程において、ウエハや粘着シートの切断を困難にすることがない。   Furthermore, when cutting an adhesive sheet that does not have a substrate, it is not necessary to cut two layers with different hardness, elongation, etc. when the blade cuts, so that the blade is subjected to the same force and the same stress. Since the adhesive sheet can be cut by moving in the layer direction of the adhesive sheet, the force on the blade changes at the interface of the layers as in the case of two layers, so It is possible to prevent so-called lumps from adhering to the blade or the adhesive sheet, and the blade or adhesive sheet to which the lumps adhere does not make it difficult to cut the wafer or the adhesive sheet in subsequent processes. .

本発明の基材層が存在しない１層の粘着シートはウレタンポリマーとアクリル系ポリマーを主剤とした粘着シートであることが好ましい。粘着シートがウレタンポリマーとアクリル系モノマー重合性化合物を主剤としたポリマーからなる紫外線硬化型の１層からなるタイプであると、通常の粘着シート製造工程でみられるような基材製膜時の延伸工程や基材への粘着剤直写あるいは転写後の貼り合せ時の製造工程の残留応力が発生せず、ウエハを極薄まで研削した時に上記のようにウエハの反りを低下させることができる。   The one-layer pressure-sensitive adhesive sheet in which the base material layer of the present invention does not exist is preferably a pressure-sensitive adhesive sheet mainly composed of a urethane polymer and an acrylic polymer. Stretching at the time of film formation of a base material as seen in a normal pressure-sensitive adhesive sheet production process, when the pressure-sensitive adhesive sheet is a type consisting of one layer of an ultraviolet curable type consisting of a polymer mainly composed of a urethane polymer and an acrylic monomer polymerizable compound Residual stress is not generated in the manufacturing process when the adhesive is directly copied to the process or the substrate or bonded after transfer, and the warpage of the wafer can be reduced as described above when the wafer is ground to an extremely thin thickness.

また半導体ウエハ裏面研削後に１層からなる粘着シートを半導体ウエハから剥離する際、基材及び粘着剤層の界面が存在しないため、剥離時に基材及び粘着剤の層間で剥離してしまいパターン面に糊残りが発生するリスクがなくなる効果がある。
本発明の粘着シートにて使用されるアクリルウレタン樹脂を得る方法としては、アクリル系モノマーにウレタンポリマーを溶解させ、これを重合することにより得たアクリル樹脂とウレタン樹脂のブレンドでもよく、ウレタンポリマーに不飽和結合を導入しておき、この不飽和結合がアクリルモノマーと反応することにより得たアクリルとウレタンポリマーとの共重合体でもよい。 In addition, when the adhesive sheet consisting of one layer is peeled from the semiconductor wafer after grinding the back surface of the semiconductor wafer, there is no interface between the base material and the pressure-sensitive adhesive layer. This has the effect of eliminating the risk of adhesive residue.
As a method of obtaining the acrylic urethane resin used in the pressure-sensitive adhesive sheet of the present invention, a blend of an acrylic resin and a urethane resin obtained by dissolving a urethane polymer in an acrylic monomer and polymerizing the urethane polymer may be used. A copolymer of acrylic and urethane polymers obtained by introducing an unsaturated bond and reacting this unsaturated bond with an acrylic monomer may also be used.

上述したとおり、本発明の粘着シートは製造工程での粘着シートで残留する応力はほとんどなくなるが、粘着シートをウエハへ貼付する際に応力が残留する。また1層であり、基材層を持たないため、パターンへの追従性を考慮すると１０％伸張時に応力緩和率が４０％以上あることが望ましい。応力緩和率が４０％以上あることで、貼付時の応力の影響によるウエハの反りも抑制できる。
また通常の粘着剤は引張弾性率が１ＭＰａ以下がほとんどであるが、応力緩和率は４０％以下程度と小さく、ウエハパターンに貼付後に経時で追従していたパターンから浮いてくる傾向がある。しかし、１層からなり１０％伸張時の応力緩和率が４０％以上ある粘着シートは経時での浮きが小さくなる。 As described above, the pressure-sensitive adhesive sheet of the present invention has almost no residual stress in the pressure-sensitive adhesive sheet in the production process, but stress remains when the pressure-sensitive adhesive sheet is stuck to a wafer. Further, since it is a single layer and does not have a base material layer, it is desirable that the stress relaxation rate is 40% or more when stretched by 10% in consideration of the followability to the pattern. When the stress relaxation rate is 40% or more, the warpage of the wafer due to the influence of stress at the time of sticking can be suppressed.
Further, the ordinary adhesive has a tensile modulus of 1 MPa or less in most cases, but the stress relaxation rate is as small as about 40% or less, and tends to float from a pattern that has been followed over time after being attached to the wafer pattern. However, a pressure-sensitive adhesive sheet that is composed of one layer and has a stress relaxation rate of 40% or more when stretched by 10% is less likely to float over time.

１層の粘着シートの厚さは５μｍ〜１０００μｍであることが好ましく、より好ましくは１０μｍ〜５００μｍ、さらに好ましくは３０μｍ〜２５０μｍである。   The thickness of the single-layer adhesive sheet is preferably 5 μm to 1000 μm, more preferably 10 μm to 500 μm, and still more preferably 30 μm to 250 μm.

１層の粘着シートの厚みがこのような範囲にある場合、半導体ウエハ裏面研削時に表面を十分に保護することができる。１層の粘着シートが５μｍ未満の場合、ウエハ表面が小さい凹凸でも追従し、保護する事ができずに研削時に割れてしまう場合がある。また、１層の粘着シートが１０００μｍを超える場合は、貼付後のテープカット性及び装置での作業性の面で好ましくない。   When the thickness of the single-layer pressure-sensitive adhesive sheet is in such a range, the surface can be sufficiently protected during grinding of the back surface of the semiconductor wafer. When the pressure-sensitive adhesive sheet of one layer is less than 5 μm, the wafer surface may follow even small irregularities and cannot be protected and may break during grinding. Moreover, when the adhesive sheet of 1 layer exceeds 1000 micrometers, it is unpreferable in terms of the tape cut property after sticking, and the workability | operativity with an apparatus.

本発明の粘着シートは、両面の粘着力が同じでも良いが、異なっていても良い。同じ粘着力とする場合には、ダイシング用の保護シートや、粘着シートの両面の粘着力に違いが現れるような対象物である場合等に使用できる。
前記粘着シートの両面の粘着力を異なるものとするために、片面のタックを消失させてその面のみを非粘着化処理することができる。特に好ましいのは片面のみの表面に凹凸を形成したり、シリカ粒子等を付着させることによる表面処理を施すことで粘着力を低下させて、弱粘着性とすることである。 The pressure-sensitive adhesive sheet of the present invention may have the same adhesive strength on both sides, but may be different. In the case of the same adhesive force, it can be used for a dicing protective sheet or an object that shows a difference in adhesive force between both surfaces of the adhesive sheet.
In order to make the adhesive force of both surfaces of the adhesive sheet different, the tack on one side can be eliminated and only the surface can be non-adhesive. It is particularly preferable to reduce the adhesive strength by forming irregularities on the surface of only one surface or to apply a surface treatment by attaching silica particles or the like to make it weakly adhesive.

１層からなる粘着シートの場合、片面を非粘着化処理しないと半導体ウエハの搬送時に搬送アームやテーブルに密着して貼り付いてしまうことが懸念されるため、このような場合には、半導体ウエハ保護用粘着シートが貼り付くことなく、半導体ウエハ裏面研削工程及び研削後も搬送することができるように非粘着化処理することが望ましい。   In the case of a single-layer adhesive sheet, if one side is not detackified, there is a concern that the semiconductor wafer may stick to and adhere to the transfer arm or table when the semiconductor wafer is transferred. It is desirable to perform the non-adhesion treatment so that the protective adhesive sheet can be transported without being attached to the semiconductor wafer back surface grinding step and after grinding.

本発明の半導体ウエハ保護用粘着シートは、厚み精度の良いセパレータ（特にＰＥＴセパレータ等）に紫外線硬化型プレポリマーを通常塗工し、例えば塗工面を凹凸セパレータでカバーした状態で紫外線を照射することにより、凹凸セパレータの凹凸を粘着シート片面に転写する形で、片面のみを非粘着化あるいは弱粘着化することができる。
また、粘着シートの片面をフッ素化処理する等により、その面を弱粘着化あるいは非粘着化することができる。 The pressure-sensitive adhesive sheet for protecting a semiconductor wafer according to the present invention is usually obtained by applying an ultraviolet curable prepolymer to a separator having a good thickness accuracy (particularly, a PET separator), and irradiating ultraviolet rays with the coated surface covered with an uneven separator, for example. Thus, the unevenness of the uneven separator can be transferred to one side of the pressure-sensitive adhesive sheet, and only one side can be made non-adhesive or weakly adhesive.
Moreover, the one surface of the pressure-sensitive adhesive sheet can be weakly or non-tacky by, for example, fluorinating the surface.

（粘着剤）
粘着シートは、粘着剤であるベースポリマーの組成、架橋剤の種類、配合比などを適宜に組み合わせて調整する。たとえば、ベースポリマーのＴｇ、架橋密度をコントロールすることで粘着シートの初期弾性率や粘着力を制御することが可能である。 (Adhesive)
The pressure-sensitive adhesive sheet is adjusted by appropriately combining the composition of the base polymer that is a pressure-sensitive adhesive, the type of crosslinking agent, the blending ratio, and the like. For example, it is possible to control the initial elastic modulus and adhesive strength of the pressure-sensitive adhesive sheet by controlling the Tg and crosslink density of the base polymer.

粘着シートとしては、たとえば、紫外線硬化型のものを使用できる。なかでも、半導体ウエハヘの接着性、剥離後の半導体ウエハの超純水やアルコール等の有機溶剤による清浄洗浄性などの点から、ウレタンポリマーとビニル系ポリマーとを有効成分とすること、あるいはウレタンポリマーとビニル系モノマーの共重合体からなるものが好ましい。   As the pressure-sensitive adhesive sheet, for example, an ultraviolet curable sheet can be used. In particular, urethane polymer and vinyl polymer are used as active ingredients from the viewpoints of adhesion to semiconductor wafers, cleanability of semiconductor wafers after peeling with organic solvents such as alcohol and alcohol, or urethane polymers. And a copolymer of vinyl monomers are preferred.

ウレタンポリマーの組成、ビニル系ポリマーやビニル系モノマーの種類や組成、ウレタンポリマーとビニル系ポリマーとの配合比等を適宜選択することによって、また、さらに架橋剤等を適宜組合せることによって、様々な特性を有する粘着シートを得ることができる。   By appropriately selecting the composition of the urethane polymer, the type and composition of the vinyl polymer and the vinyl monomer, the blending ratio of the urethane polymer and the vinyl polymer, etc. A pressure-sensitive adhesive sheet having characteristics can be obtained.

本発明において粘着シートは、例えば、ウレタンポリマーの存在下で、ビニル系モノマーを溶液重合やエマルジョン重合することによって得ることができる。粘着シートを構成するビニル系ポリマーは、アクリル系ポリマーであることが好ましく、この場合には、アクリル系モノマーを溶液重合等することによってアクリルウレタン樹脂からなる材料を得ることができる。   In the present invention, the pressure-sensitive adhesive sheet can be obtained, for example, by subjecting a vinyl monomer to solution polymerization or emulsion polymerization in the presence of a urethane polymer. The vinyl polymer constituting the pressure-sensitive adhesive sheet is preferably an acrylic polymer. In this case, a material comprising an acrylic urethane resin can be obtained by solution polymerization of an acrylic monomer.

本発明における粘着シートは、ラジカル重合性モノマーとしてのビニル系モノマーを希釈剤として、このラジカル重合性モノマー中でウレタンポリマーを形成し、ラジカル重合性モノマーとウレタンポリマーとを主成分として含む混合物をセパレータに塗布し、放射線を照射して硬化させることにより、形成してもよい。ここで、ラジカル重合性モノマーとしては、ラジカル重合可能な不飽和二重結合を有するものが使用され、ビニル系モノマー等が使用されるが、反応性の点からは、アクリル系モノマーが好ましい。   The pressure-sensitive adhesive sheet according to the present invention uses a vinyl monomer as a radical polymerizable monomer as a diluent, forms a urethane polymer in the radical polymerizable monomer, and separates a mixture containing the radical polymerizable monomer and the urethane polymer as main components. You may form by apply | coating to, and irradiating a radiation and making it harden | cure. Here, as the radically polymerizable monomer, one having an unsaturated double bond capable of radical polymerization is used, and a vinyl monomer or the like is used. From the viewpoint of reactivity, an acrylic monomer is preferable.

具体的には、（ａ）ポリオールとジイソシアネートとを反応させてウレタンポリマーを合成した後、この反応生成物をアクリル系モノマーに溶解させて粘度調整を行い、これを第一フィルムに塗工した後、低圧水銀ランプ等を用いて硬化させることにより、ウレタン−アクリル複合材料を得ることができる。そして、そのウレタンポリマーを末端にビニル基を有するポリマーとすることにより、アクリル系モノマーと共重合させることも可能である。
（ｂ）ポリオールをアクリル系モノマーに溶解させた後、ジイソシアネートを反応させてウレタンポリマーを合成すると共に粘度調整を行い、これを第一フィルムに塗工した後、低圧水銀ランプ等を用いて硬化させることにより、ウレタン−アクリル複合材料を得ることもできる。その際に、例えば水酸基含有ビニル系モノマーを添加することによって末端にビニル基を有するウレタンポリマーを合成しておくと、そのビニル基がアクリル系モノマーを共重合することが可能となる。 Specifically, (a) after reacting a polyol and diisocyanate to synthesize a urethane polymer, this reaction product is dissolved in an acrylic monomer to adjust the viscosity, and this is applied to the first film The urethane-acrylic composite material can be obtained by curing using a low-pressure mercury lamp or the like. And it can also be copolymerized with an acrylic monomer by making the urethane polymer into a polymer having a vinyl group at the terminal.
(B) After dissolving the polyol in the acrylic monomer, the diisocyanate is reacted to synthesize the urethane polymer and the viscosity is adjusted. After coating this on the first film, it is cured using a low-pressure mercury lamp or the like. Thus, a urethane-acrylic composite material can also be obtained. At that time, for example, if a urethane polymer having a vinyl group at the terminal is synthesized by adding a hydroxyl group-containing vinyl monomer, the vinyl group can copolymerize the acrylic monomer.

これらの方法では、アクリル系モノマーをウレタン合成中に一度に添加してもよいし、何回かに分割して添加してもよい。また、ジイソシアネートをアクリル系モノマーに溶解させた後、ポリオールを反応させてもよい。
ここで、（ａ）の方法によれば、ポリオールとジイソシアネートとの反応により生成するポリウレタンの分子量が高くなると、アクリル系モノマーに溶解させることが困難になるので、ポリウレタンの分子量が必然的に限定されてしまう、という欠点がある。
一方、（ｂ）の方法によれば、分子量が限定されるということはなく、高分子量のポリウレタンを生成することもできるので、最終的に得られるウレタンの分子量を任意の大きさに設計することができる。
また、（ｃ）予め、別途調整したウレタンポリマーをアクリル系モノマー中に溶解し、これを第一フィルムに塗工した後、低圧水銀ランプ等を用いて硬化させることにより、ウレタン−アクリル樹脂材料を得ることもできる。 In these methods, the acrylic monomer may be added all at once during the urethane synthesis, or may be added in several divided portions. Alternatively, the polyol may be reacted after the diisocyanate is dissolved in the acrylic monomer.
Here, according to the method (a), if the molecular weight of the polyurethane produced by the reaction between the polyol and the diisocyanate increases, it becomes difficult to dissolve in the acrylic monomer, so that the molecular weight of the polyurethane is necessarily limited. There is a drawback that.
On the other hand, according to the method (b), the molecular weight is not limited, and a high-molecular-weight polyurethane can be produced. Therefore, the molecular weight of the finally obtained urethane should be designed to an arbitrary size. Can do.
In addition, (c) a urethane polymer separately prepared in advance is dissolved in an acrylic monomer, applied to the first film, and then cured using a low-pressure mercury lamp or the like to obtain a urethane-acrylic resin material. It can also be obtained.

（アクリル系モノマー）
本発明に好ましく用いられるアクリル系モノマーとしては、例えば、（メタ）アクリル酸、（メタ）アクリル酸メチル、（メタ）アクリル酸エチル、（メタ）アクリル酸プロピル、（メタ）アクリル酸ブチル、（メタ）アクリル酸ペンチル、（メタ）アクリル酸ヘキシル、（メタ）アクリル酸２−エチルヘキシル、（メタ）アクリル酸オクチル、（メタ）アクリル酸イソオクチル、（メタ）アクリル酸ノニル、（メタ）アクリル酸イソノニル、（ メタ）アクリル酸イソボルニル、等を挙げることができる。
これらのエステルと共に、マレイン酸、イタコン酸等のカルボキシル基を有するモノマーや、２−ヒドロキシエチルアクリレート、２−ヒドロキシエチルメタクリレート、４−ヒドロキシブチル（メタ）アクリレート、６−ヒドロキシヘキシル（メタ）アクリレート等のヒドロキシル基を有するモノマーを用いることができる。 (Acrylic monomer)
Examples of the acrylic monomer preferably used in the present invention include (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, (meth ) Pentyl acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, nonyl (meth) acrylate, isononyl (meth) acrylate, ( And meth) acrylic acid isobornyl.
Along with these esters, monomers having carboxyl groups such as maleic acid and itaconic acid, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, etc. Monomers having hydroxyl groups can be used.

また、酢酸ビニル、プロピオン酸ビニル、スチレン、アクリルアミド、メタクリルアミド、マレイン酸のモノまたはジエステル、及びその誘導体、Ｎ−メチロールアクリルアミド、グリシジルアクリレート、グリシジルメタクリレート、Ｎ，Ｎ−ジメチルアミノエチルアクリレート、Ｎ，Ｎ−ジメチルアミノプロピルメタクリルアミド、２−ヒドロキシプロピルアクリレート、アクリロイルモルホリン、Ｎ，Ｎ−ジメチルアクリルアミド、Ｎ，Ｎ −ジエチルアクリルアミド、イミドアクリレート、Ｎ−ビニルピロリドン、オリゴエステルアクリレート、ε−カプロラクトンアクリレート、ジシクロペンタニル（メタ）アクリレート、ジシクロペンテニル（メタ）アクリレート、メトキシ化シクロドデカトリエンアクリレート、メトキシエチルアクリレート等のモノマーを共重合してもよい。なお、これら共重合されるモノマーの種類や使用量は、複合フィルムの特性等を考慮して適宜決定される。
本発明においては、必要に応じ、特性を損なわない範囲内で他の多官能モノマーを添加することもできる。多官能モノマーとしては、エチレングリコールジ（メタ）アクリレート、プロピレングリコールジ（メタ）アクリレート、ヘキサンジオールジ（メタ）アクリレート、ネオペンチルグリコールジ（メタ）アクリレート、トリメチロールプロパントリ（メタ）アクリレート、ペンタエリスリトールトリ（メタ）アクリレート、ジペンタエリスリトールヘキサ（メタ）アクリレート、ウレタンアクリレート、エポキシアクリレート、ポリエステルアクリレート等を挙げることができ、特に好ましくは、トリメチロールプロパントリ（メタ）アクリレートである。これらのモノマーも、本発明に係るラジカル重合性モノマーに含まれる。
これらのラジカル重合性モノマーは、ウレタンとの相溶性、放射線等の光硬化時の重合性や、得られる高分子量体の特性を考慮して、種類、組合せ、使用量等が適宜決定される。 Further, vinyl acetate, vinyl propionate, styrene, acrylamide, methacrylamide, mono- or diester of maleic acid, and derivatives thereof, N-methylolacrylamide, glycidyl acrylate, glycidyl methacrylate, N, N-dimethylaminoethyl acrylate, N, N -Dimethylaminopropyl methacrylamide, 2-hydroxypropyl acrylate, acryloylmorpholine, N, N-dimethylacrylamide, N, N-diethylacrylamide, imide acrylate, N-vinylpyrrolidone, oligoester acrylate, ε-caprolactone acrylate, dicyclopenta Nyl (meth) acrylate, dicyclopentenyl (meth) acrylate, methoxylated cyclododecatriene acrylate, methoxyethyl Monomers may be copolymerized with such acrylate. Note that the types and amounts of the monomers to be copolymerized are appropriately determined in consideration of the characteristics of the composite film.
In the present invention, if necessary, other polyfunctional monomers can be added within a range not impairing the characteristics. Polyfunctional monomers include ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, and pentaerythritol. Examples include tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, urethane acrylate, epoxy acrylate, polyester acrylate, and the like, and trimethylolpropane tri (meth) acrylate is particularly preferable. These monomers are also included in the radical polymerizable monomer according to the present invention.
These radically polymerizable monomers are appropriately determined in terms of type, combination, amount of use, and the like in consideration of compatibility with urethane, polymerizability at the time of photocuring such as radiation, and characteristics of the high molecular weight obtained.

（ウレタンポリマー）
ウレタンポリマーは、ポリオールとポリイソシアネートとを反応させて得られる。イソシアネートとポリオールの水酸基との反応には、触媒を用いても良い。例えば、ジブチルすずジラウレート、オクトエ酸すず、１，４−ジアザビシクロ（２，２，２）オクタン等の、ウレタン反応において一般的に使用される触媒を用いることができる。 (Urethane polymer)
The urethane polymer is obtained by reacting a polyol and a polyisocyanate. A catalyst may be used for the reaction between the isocyanate and the hydroxyl group of the polyol. For example, a catalyst generally used in a urethane reaction, such as dibutyltin dilaurate, tin octoate, or 1,4-diazabicyclo (2,2,2) octane, can be used.

ポリオールとしては、１分子中に２個またはそれ以上の水酸基を有するものが望ましい。低分子量のポリオールとしては、エチレングリコール、ジエチレングリコール、プロピレングリコール、ブチレングリコール、ヘキサメチレングリコール等の２価のアルコール、トリメチロールプロパン、グリセリン等の３価のアルコール、またはペンタエリスリトール等の４価のアルコール等が挙げられる。
また、高分子量のポリオールとしては、エチレンオキサイド、プロピレンオキサイド、テトラヒドロフラン等を付加重合して得られるポリエーテルポリオール、あるいは上述の２ 価のアルコール、ジプロピレングリコール、１，４−ブタンジオール、１，６−ヘキサンジオール、ネオペンチルグリコール等のアルコールとアジピン酸、アゼライン酸、セバチン酸等の２価の塩基酸との重縮合物からなるポリエステルポリオールや、アクリルポリオール、カーボネートポリオール、エポキシポリオール、カプロラクトンポリオール等が挙げられる。これらの中では、ポリエーテルポリオール、ポリエステルポリオールが好ましい。
アクリルポリオールとしてはヒドロキシエチル（メタ）アクリレート、ヒドロキシプロピル（メタ）アクリレート等の水酸基を有するモノマーの共重合体の他、水酸基含有物とアクリル系モノマーとの共重合体等が挙げられる。エポキシポリオールとしてはアミン変性エポキシ樹脂等がある。これらのポリオール類は単独あるいは併用して使用することができる。強度を必要とする場合には、トリオールによる架橋構造を導入したり、低分子量ジオールによるウレタンハードセグメント量を増加させると効果的である。伸びを重視する場合には、分子量の大きなジオールを単独で使用することが好ましい。また、ポリエーテルポリオールは、一般的に、安価で耐水性が良好であり、ポリエステルポリオールは、強度が高い。本発明においては、用途や目的に応じて、ポリオールの種類や量を自由に選択することができ、また、塗布するフィルムの特性、イソシアネートとの反応性、アクリルとの相溶性などの観点からもポリオールの種類、分子量や使用量を適宜選択することができる。 As the polyol, those having two or more hydroxyl groups in one molecule are desirable. Examples of the low molecular weight polyol include divalent alcohols such as ethylene glycol, diethylene glycol, propylene glycol, butylene glycol, and hexamethylene glycol, trivalent alcohols such as trimethylolpropane and glycerin, and tetravalent alcohols such as pentaerythritol. Is mentioned.
Moreover, as a high molecular weight polyol, polyether polyol obtained by addition polymerization of ethylene oxide, propylene oxide, tetrahydrofuran or the like, or the above-mentioned dihydric alcohol, dipropylene glycol, 1,4-butanediol, 1,6 -Polyester polyols composed of polycondensates of alcohols such as hexanediol and neopentyl glycol and divalent basic acids such as adipic acid, azelaic acid and sebacic acid, acrylic polyols, carbonate polyols, epoxy polyols, caprolactone polyols, etc. Can be mentioned. In these, polyether polyol and polyester polyol are preferable.
Examples of the acrylic polyol include a copolymer of a monomer having a hydroxyl group such as hydroxyethyl (meth) acrylate and hydroxypropyl (meth) acrylate, and a copolymer of a hydroxyl group-containing substance and an acrylic monomer. Examples of the epoxy polyol include an amine-modified epoxy resin. These polyols can be used alone or in combination. When strength is required, it is effective to introduce a cross-linked structure with triol or increase the amount of urethane hard segment with low molecular weight diol. When importance is attached to elongation, a diol having a large molecular weight is preferably used alone. Polyether polyols are generally inexpensive and have good water resistance, and polyester polyols have high strength. In the present invention, the kind and amount of the polyol can be freely selected according to the use and purpose, and also from the viewpoint of the characteristics of the film to be applied, reactivity with isocyanate, compatibility with acrylic, and the like. The kind of polyol, molecular weight, and usage-amount can be selected suitably.

ポリイソシアネートとしては芳香族、脂肪族、脂環族のジイソシアネート、これらのジイソシアネートの二量体、三量体等が挙げられる。芳香族、脂肪族、脂環族のジイソシアネートとしては、トリレンジイソシアネート、ジフェニルメタンジイソシアネート、ヘキサメチレンジイソシアネート、キシリレンジイソシアネート、水添キシリレンジイソシアネート、イソホロンジイソシアネート、水添ジフェニルメタンジイソシアネート、１，５− ナフチレンジイソシアネート、１，３−フェニレンジイソシアネート、１，４−フェニレンジイソシアネート、ブタン−１，４−ジイソシアネート、２，２，４−トリメチルヘキサメチレンジイソシアネート、２，４，４−トリメチルヘキサメチレンジイソシアネート、シクロヘキサン−１，４−ジイソシアネート、ジシクロヘキシルメタン−４，４−ジイソシアネート、１，３−ビス（イソシアネートメチル）シクロヘキサン、メチルシクロヘキサンジイソシアネート、ｍ−テトラメチルキシリレンジイソシアネート等が挙げられる。
また、これらの二量体、三量体や、ポリフェニルメタンポリイソシアネートが用いられる。三量体としては、イソシアヌレート型、ビューレット型、アロファネート型等が挙げられ、適宜、使用することができる。
これらのポリイソシアネート類は単独あるいは併用で使用することができる。ウレタン反応性、アクリルとの相溶性などの観点から、ポリイソシアネートの種類、組合せ等を適宜選択すればよい。
本発明においては、ウレタンポリマーが、ヘキサメチレンジイソシアネート（ＨＤＩ）、水添トリレンジイソシアネート（ＨＴＤＩ）、水添４，４−ジフェニルメタンジイソシアネート（ＨＭＤＩ）、イソホロンジイソシアネート（ＩＰＤＩ）、および、水添キシレンジイソシアネート（ＨＸＤＩ）からなる群から選ばれる少なくとも１種類のジイソシアネートを用いて形成されることが好ましい。 Examples of the polyisocyanate include aromatic, aliphatic and alicyclic diisocyanates, dimers and trimers of these diisocyanates. Aromatic, aliphatic, and alicyclic diisocyanates include tolylene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, isophorone diisocyanate, hydrogenated diphenylmethane diisocyanate, 1,5-naphthylene diisocyanate. 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, butane-1,4-diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, cyclohexane-1,4 -Diisocyanate, dicyclohexylmethane-4,4-diisocyanate, 1,3-bis (isocyanatemethyl) cyclohexane, methyl Examples include rucyclohexane diisocyanate and m-tetramethylxylylene diisocyanate.
Moreover, these dimers, trimers, and polyphenylmethane polyisocyanate are used. Examples of the trimer include isocyanurate type, burette type, and allophanate type, and can be used as appropriate.
These polyisocyanates can be used alone or in combination. From the viewpoints of urethane reactivity, compatibility with acrylic, and the like, the type and combination of polyisocyanates may be appropriately selected.
In the present invention, the urethane polymer contains hexamethylene diisocyanate (HDI), hydrogenated tolylene diisocyanate (HTDI), hydrogenated 4,4-diphenylmethane diisocyanate (HMDI), isophorone diisocyanate (IPDI), and hydrogenated xylene diisocyanate ( It is preferably formed using at least one diisocyanate selected from the group consisting of HXDI).

上記ウレタンポリマーの合成にあたり、水酸基含有ビニルモノマーとして、水酸基含有アクリルモノマーを添加してもよい。水酸基含有アクリルモノマーを添加することにより、ウレタンプレポリマーの分子末端に（メタ）アクリロイル基を導入することができ、アクリル系モノマーとの共重合性が付与され、ウレタン成分とアクリル成分との相溶性が高まり、破断強度などのＳ−Ｓ特性の向上を図ることもできる。水酸基含有アクリルモノマーとしては、ヒドロキシエチル（メタ）アクリレート、ヒドロキシプロピル（メタ）アクリレート、ヒドロキシブチル（メタ）アクリレート、ヒドロキシへキシル（メタ）アクリレート等が用いられる。水酸基含有アクリルモノマーの使用量は、ウレタンポリマー１００重量部に対して、０．１〜１０重量部であることが好ましく、更に好ましくは１〜５重量部である。
このようにして得られたウレタンアクリル樹脂はウレタン樹脂とアクリル樹脂のブレンドではなく、アクリル樹脂の主鎖にウレタンポリマー末端の（メタ）アクリロイル基が共重合することによって一体の重合体となる。 In synthesizing the urethane polymer, a hydroxyl group-containing acrylic monomer may be added as a hydroxyl group-containing vinyl monomer. By adding a hydroxyl group-containing acrylic monomer, it is possible to introduce a (meth) acryloyl group at the molecular end of the urethane prepolymer, imparting copolymerization with an acrylic monomer, and compatibility between the urethane component and the acrylic component. And SS characteristics such as breaking strength can be improved. As the hydroxyl group-containing acrylic monomer, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, hydroxyhexyl (meth) acrylate, or the like is used. It is preferable that the usage-amount of a hydroxyl-containing acrylic monomer is 0.1-10 weight part with respect to 100 weight part of urethane polymers, More preferably, it is 1-5 weight part.
The urethane acrylic resin thus obtained is not a blend of urethane resin and acrylic resin, but becomes an integral polymer by copolymerization of the (meth) acryloyl group at the end of the urethane polymer with the main chain of the acrylic resin.

本発明において、ウレタンポリマーを形成するためのポリオール成分とポリイソシアネート成分の使用量は特に限定されるものではないが、例えば、ポリオール成分の使用量は、ポリイソシアネート成分に対し、ＮＣＯ／ＯＨ（当量比）が０．８以上であることが好ましく、０．８以上、３．０以下であることがさらに好ましい。ＮＣＯ／ＯＨが０．８未満では、ウレタンポリマーの分子鎖長を充分に延ばすことができず、フィルム強度や、伸びが低下しやすい。また、ＮＣＯ／ＯＨが３．０以下であれば、柔軟性を十分確保することができる。   In the present invention, the use amount of the polyol component and the polyisocyanate component for forming the urethane polymer is not particularly limited. For example, the use amount of the polyol component is NCO / OH (equivalent to the polyisocyanate component). Ratio) is preferably 0.8 or more, more preferably 0.8 or more and 3.0 or less. When NCO / OH is less than 0.8, the molecular chain length of the urethane polymer cannot be extended sufficiently, and the film strength and elongation tend to decrease. Moreover, if NCO / OH is 3.0 or less, sufficient flexibility can be ensured.

（粘着剤に添加可能な添加剤）
粘着シートを構成する粘着剤層には、必要に応じて、通常使用される添加剤、例えば紫外線吸収剤、老化防止剤、充填剤、顔料、着色剤、難燃剤、帯電防止剤などを本発明の効果を阻害しない範囲内で添加することができる。これらの添加剤は、その種類に応じて通常の量で用いられる。
これらの添加剤は、ポリイソシアネートとポリオールとの重合反応前に、あらかじめ加えておいてもよいし、ウレタンポリマーと反応性モノマーとを重合させる前に、添加してもよい。また、塗工時の粘度調整のため、少量の溶剤を加えてもよい。溶剤としては、通常使用される溶剤の中から適宜選択することができるが、例えば、酢酸エチル、トルエン、クロロホルム、ジメチルホルムアミド等が挙げられる。 (Additives that can be added to adhesives)
In the pressure-sensitive adhesive layer constituting the pressure-sensitive adhesive sheet, the present invention contains, as necessary, commonly used additives such as UV absorbers, anti-aging agents, fillers, pigments, colorants, flame retardants, antistatic agents and the like. It can be added within a range that does not impair the effect. These additives are used in normal amounts depending on the type.
These additives may be added in advance before the polymerization reaction between the polyisocyanate and the polyol, or may be added before the urethane polymer and the reactive monomer are polymerized. Moreover, you may add a small amount of solvent for the viscosity adjustment at the time of coating. The solvent can be appropriately selected from commonly used solvents, and examples thereof include ethyl acetate, toluene, chloroform, dimethylformamide and the like.

（粘着シートの製造）
本発明においては、上述したように、例えば、ラジカル重合性モノマー中でポリオールとイソシアネートの反応を行い、ウレタンポリマーとラジカル重合性モノマーとの混合物をセパレータに塗布し、光重合開始剤の種類等に応じて、α線、β線、γ線、中性子線、電子線等の電離性放射線や紫外線等の放射線、可視光等を照射することにより、光硬化して粘着シートを形成することができる。
この際、酸素による重合阻害を避けるために、セパレータ上に塗布したウレタンポリマーとラジカル重合性モノマーとの混合物の上に、剥離処理したシートをのせて酸素を遮断してもよいし、不活性ガスを充填した容器内に基材を入れて、酸素濃度を下げてもよい。本発明において、放射線等の種類や照射に使用されるランプの種類等は適宜選択することができ、蛍光ケミカルランプ、ブラックライト、殺菌ランプ等の低圧ランプや、メタルハライドランプ、高圧水銀ランプ等の高圧ランプ等を用いることができる。紫外線などの照射量は、要求されるフィルムの特性に応じて、任意に設定することができる。 (Manufacture of adhesive sheet)
In the present invention, as described above, for example, a polyol and an isocyanate are reacted in a radical polymerizable monomer, a mixture of a urethane polymer and a radical polymerizable monomer is applied to a separator, and the type of photopolymerization initiator is changed. Accordingly, by irradiation with ionizing radiation such as α rays, β rays, γ rays, neutron rays, and electron beams, radiation such as ultraviolet rays, visible light, etc., it can be photocured to form an adhesive sheet.
At this time, in order to avoid polymerization inhibition due to oxygen, the release-treated sheet may be placed on a mixture of a urethane polymer and a radical polymerizable monomer coated on the separator to block oxygen, or an inert gas. The substrate may be placed in a container filled with oxygen to lower the oxygen concentration. In the present invention, the type of radiation and the type of lamp used for irradiation can be selected as appropriate, such as a low-pressure lamp such as a fluorescent chemical lamp, a black light and a sterilization lamp, a high-pressure such as a metal halide lamp and a high-pressure mercury lamp. A lamp or the like can be used. Irradiation amounts such as ultraviolet rays can be arbitrarily set according to required film characteristics.

一般的には、紫外線の照射量は、１００〜５，０００ｍＪ／ｃｍ２、好ましくは１， ０００〜４，０００ｍＪ／ｃｍ２、更に好ましくは２，０００〜３，０００ｍＪ／ｃｍ２ である。紫外線の照射量が１００ｍＪ／ｃｍ２より少ないと、十分な重合率が得られないことがあり、５，０００ｍＪ／ｃｍ２より多いと、劣化の原因となることがある。
また、紫外線照射する際の温度については特に限定があるわけではなく任意に設定することができるが、温度が高すぎると重合熱による停止反応が起こり易くなり、特性低下の原因となりやすいので、通常は７０℃以下であり、好ましくは５０℃以下であり、更に好ましくは３０℃以下である。 Generally, the dose of ultraviolet rays, 100~5,000mJ / cm 2, preferably 1, 000~4,000mJ / cm 2, more preferably from 2,000~3,000mJ / cm 2. When the irradiation amount of ultraviolet rays is less than 100 mJ / cm 2 , a sufficient polymerization rate may not be obtained, and when it is more than 5,000 mJ / cm 2 , deterioration may be caused.
In addition, the temperature at the time of ultraviolet irradiation is not particularly limited and can be arbitrarily set. However, if the temperature is too high, a termination reaction due to the heat of polymerization is likely to occur, which tends to cause deterioration of characteristics. Is 70 ° C. or lower, preferably 50 ° C. or lower, more preferably 30 ° C. or lower.

ウレタンポリマーとラジカル重合性モノマーとを主成分とする混合物には、光重合開始剤が含まれる。光重合開始剤としては、ベンゾインメチルエーテル、ベンゾインイソプロピルエーテル等のベンゾインエーテル、アニソールメチルエーテル等の置換ベンゾインエーテル、２，２−ジエトキシアセトフェノン、２，２−ジメトキシ−２−フェニルアセトフェノン等の置換アセトフェノン、１−ヒドロキシ−シクロヘキシル−フェニル−ケトン、２−メチル−２−ヒドロキシプロピオフェノン等の置換アルファーケトール、２−ナフタレンスルフォニルクロライド等の芳香族スルフォニルクロライド、１−フェニル−１，１ −プロパンジオン−２−（ｏ−エトキシカルボニル）−オキシム等の光活性オキシムが好ましく用いられる。
本発明においては、分子内に水酸基を有する光重合開始剤を用いることが特に望ましい。ポリオールとポリイソシアネートを反応させてウレタンポリマーを形成する際に、分子内に水酸基を有する光重合開始剤を共存させることで、ウレタンポリマー中に光重合開始剤を採り込ませることができる。これにより、放射線を照射して硬化させるときにウレタン−アクリルのブロックポリマーを生成することができる。この効果によって伸びと強度を向上させることができるものと推定される。 The mixture containing the urethane polymer and the radical polymerizable monomer as main components contains a photopolymerization initiator. Photopolymerization initiators include benzoin ethers such as benzoin methyl ether and benzoin isopropyl ether, substituted benzoin ethers such as anisole methyl ether, and substituted acetophenones such as 2,2-diethoxyacetophenone and 2,2-dimethoxy-2-phenylacetophenone. 1-hydroxy-cyclohexyl-phenyl-ketone, substituted alpha-ketols such as 2-methyl-2-hydroxypropiophenone, aromatic sulfonyl chlorides such as 2-naphthalenesulfonyl chloride, 1-phenyl-1,1-propanedione- Photoactive oximes such as 2- (o-ethoxycarbonyl) -oxime are preferably used.
In the present invention, it is particularly desirable to use a photopolymerization initiator having a hydroxyl group in the molecule. When a urethane polymer is formed by reacting a polyol and a polyisocyanate, a photopolymerization initiator having a hydroxyl group in the molecule is allowed to coexist, whereby the photopolymerization initiator can be incorporated into the urethane polymer. Thereby, a urethane-acrylic block polymer can be produced when cured by irradiation with radiation. It is presumed that the elongation and strength can be improved by this effect.

また粘着シートには熱膨張性微粒子が配合されていても良い。熱発泡性微粒子は、熱による熱膨張性微粒子の発泡により、接着面積が減少して剥離が容易になるものであり、熱膨張性微粒子の平均粒子径は１μｍ〜２５μｍ程度のものが好ましい。より好ましくは５μｍ〜１５μｍであり、特に１０μｍ程度のものが好ましい。熱膨張性微粒子としては、加熱下に膨張する素材を特に制限なく使用できるが、たとえば、ブタン、プロパン、ペンタンなどの如き低沸点の適宜のガス発泡性成分をインサイト重合法等により、塩化ビニリデン、アクリロニトリル等の共重合物の殻壁でカプセル化した熱膨張性マイクロカプセルを用いることができる。熱膨張性マイクロカプセルは、上記粘着剤との分散混合性に優れているなどの利点も有する。熱膨張性マイクロカプセルの市販品としては、たとえば、マイクロスフェアー（商品名：松本油脂社製）などがあげられる。   The pressure-sensitive adhesive sheet may contain thermally expandable fine particles. The thermally expandable fine particles are those in which the adhesive area decreases due to foaming of the thermally expandable fine particles due to heat, and peeling becomes easy. The average particle diameter of the thermally expandable fine particles is preferably about 1 μm to 25 μm. More preferably, it is 5 μm to 15 μm, and particularly about 10 μm is preferable. As the heat-expandable fine particles, a material that expands under heating can be used without particular limitation. For example, an appropriate gas-foaming component having a low boiling point such as butane, propane, pentane, etc. Thermally expandable microcapsules encapsulated with a shell wall of a copolymer such as acrylonitrile can be used. The heat-expandable microcapsule also has advantages such as excellent dispersion and mixing properties with the pressure-sensitive adhesive. Examples of commercially available thermal expandable microcapsules include microspheres (trade name: manufactured by Matsumoto Yushi Co., Ltd.).

上記粘着シートに対する熱膨張性微粒子（熱膨張性マイクロカプセル）の配合量は、上記粘着シートの種類に応じて、粘着剤層の粘着力を低下できる量を、適宜に決定することができるが、一般的には、ベースポリマー１００重量部に対して、１重量部〜１００重量部程度、好ましくは５重量部〜５０重量部、更に好ましくは１０重量部〜４０重量部である。   The amount of thermally expandable fine particles (thermally expandable microcapsules) to the pressure-sensitive adhesive sheet can be determined as appropriate depending on the type of the pressure-sensitive adhesive sheet, and the amount that can reduce the adhesive strength of the pressure-sensitive adhesive layer. Generally, it is about 1 to 100 parts by weight, preferably 5 to 50 parts by weight, and more preferably 10 to 40 parts by weight with respect to 100 parts by weight of the base polymer.

本発明の粘着シートの厚みは、目的等に応じて適宜選択することができる。特に精密部品の加工用に用いる場合、粘着シートは１０ 〜３００μｍであることが好ましく、さらに好ましくは５０〜２５０μｍ程度であり、その他のフィルムの場合には１０〜３００μｍであることが好ましく、さらに好ましくは３０〜２００μｍ程度である。   The thickness of the pressure-sensitive adhesive sheet of the present invention can be appropriately selected depending on the purpose and the like. In particular, when used for processing precision parts, the pressure-sensitive adhesive sheet is preferably 10 to 300 μm, more preferably about 50 to 250 μm, and other films are preferably 10 to 300 μm, more preferably. Is about 30-200 μm.

（本発明の粘着シートの使用方法）
本発明の粘着シートは、例えば半導体ウエハ等の製品を加工する際に、常法に従って用いられる。半導体ウエハの裏面を研削加工する際に該半導体ウエハ表面を保護すると共に、治具に固定するための保護シートとすることができ、あるいはダイシング時において半導体ウエハ等裏面を基板に固定するために半導体ウエハ裏面に貼る用途等に用いることもできる。
ここでは、半導体ウエハの裏面を研削加工する際に使用する例を示す。まず、テーブル上にＩＣ回路等のパターン面が上になるように半導体ウエハを載置し、そのパターン面の上に、本発明の粘着シートを、その粘着剤層が接するように重ね、圧着ロール等の押圧手段によって押圧しながら貼付する。あるいは、加圧可能な容器（例えばオートクレーブ）内に、上記のように半導体ウエハと粘着シートとを重ねたものを置いた後、容器内を加圧して半導体ウエハと粘着シートとを貼着してもよいし、これに押圧手段を併用してもよい。また、真空チャンバー内で半導体ウエハと粘着シートとを貼着してもよいし、粘着シートの基材の融点以下の温度で加熱することにより貼着してもよい。 (Usage method of the pressure-sensitive adhesive sheet of the present invention)
The pressure-sensitive adhesive sheet of the present invention is used according to a conventional method when processing a product such as a semiconductor wafer. When grinding the back surface of a semiconductor wafer, the semiconductor wafer surface can be protected and used as a protective sheet for fixing to a jig, or a semiconductor for fixing the back surface of a semiconductor wafer or the like to a substrate during dicing It can also be used for applications to be applied to the back side of the wafer.
Here, the example used when grinding the back surface of a semiconductor wafer is shown. First, a semiconductor wafer is placed on a table so that the pattern surface of an IC circuit or the like is on top, and the pressure-sensitive adhesive sheet of the present invention is stacked on the pattern surface so that the pressure-sensitive adhesive layer is in contact with the pressure roll. Affixing while pressing with a pressing means such as. Alternatively, after placing the semiconductor wafer and the pressure-sensitive adhesive sheet as described above in a pressurizable container (for example, an autoclave), the inside of the container is pressurized to adhere the semiconductor wafer and the pressure-sensitive adhesive sheet. Alternatively, pressing means may be used in combination. Further, the semiconductor wafer and the adhesive sheet may be attached in a vacuum chamber, or may be attached by heating at a temperature not higher than the melting point of the base material of the adhesive sheet.

半導体ウエハの裏面研磨加工方法としては、通常の研削方法を採用することができる。例えば、上記のようにして粘着シートを貼着した半導体ウエハの裏面を、研磨するための加工機として研削機（バックグラインド）、ＣＭＰ（Chemical Mechanical Polishing）用パッド等を用いて所望の厚さになるまで研削を行う。   As a method for polishing the back surface of the semiconductor wafer, a normal grinding method can be employed. For example, a grinding machine (back grind), a CMP (Chemical Mechanical Polishing) pad, or the like is used as a processing machine for polishing the back surface of the semiconductor wafer to which the adhesive sheet is adhered as described above to a desired thickness. Grind until

本発明に係る粘着シートに使用されるセパレータには、被着体への貼付面を保護するセパレータと場合によっては背面へ凹凸転写することで非粘着化するための凹凸のついたセパレータが必要になる。これらのセパレータの構成材料としては、紙、ポリエチレン、ポリプロピレン、ポリエチレンテレフタレート等の合成樹脂フィルム等があげられる。セパレータの表面には、粘着剤層からの剥離性を高めるため、必要に応じてシリコーン処理、長鎖アルキル処理、フッ素処理等の離型処理が施されていても良い。セパレータの厚みは、１０μｍ〜２００μｍが好ましく、より好ましくは２５μｍ〜１００μｍである。また、セパレータの厚み精度は±２μｍ以下であることが好ましい。   The separator used for the pressure-sensitive adhesive sheet according to the present invention requires a separator that protects the surface to be adhered to the adherend and, in some cases, a separator with unevenness to make it non-adhesive by transferring unevenness to the back surface. Become. Examples of the constituent material of these separators include paper, synthetic resin films such as polyethylene, polypropylene, and polyethylene terephthalate. The surface of the separator may be subjected to mold release treatment such as silicone treatment, long-chain alkyl treatment, fluorine treatment, etc., if necessary, in order to improve the peelability from the pressure-sensitive adhesive layer. The thickness of the separator is preferably 10 μm to 200 μm, more preferably 25 μm to 100 μm. Further, the thickness accuracy of the separator is preferably ± 2 μm or less.

本発明の粘着シートとウエハとの貼り合わせは、加圧可能な容器（例えばオートクレーブなど）中で、ウエハの表面と粘着シートの粘着剤層を重ね、容器内を加圧することによりウエハに貼り合わせることも出来る。この際、押圧手段により押圧しながら貼り合わせてもよい。また、真空チャンバー内で、上記と同様に貼り合わせることもできる。貼り合わせ時の条件はこれらに限定されるものではなく、貼り合わせる際に、加熱をすることもできる。   The pressure-sensitive adhesive sheet of the present invention and the wafer are bonded together in a pressurizable container (for example, an autoclave) by stacking the surface of the wafer and the pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet, and pressing the inside of the container to bond the wafer. You can also At this time, bonding may be performed while pressing with a pressing means. Moreover, it can also bond together like the above in a vacuum chamber. The conditions at the time of bonding are not limited to these, and heating can also be performed at the time of bonding.

以下に実施例を用いて、本発明を詳細に説明するが、本発明はこれに限定されるものではない。   Hereinafter, the present invention will be described in detail using examples, but the present invention is not limited thereto.

実施例１
冷却管、温度計、および攪拌装置を備えた反応容器に、アクリル系モノマーとして、アクリル酸ｔ−ブチル３０部、アクリル酸２０部、イソボルニルアクリレート８０部、光重合開始剤として、2,2-ジメトキシ-1,2-ジフェニルエタン-1-オン（商品名「イルガキュア６５１」、チバ・スペシャルティ・ケミカルズ（株）製）０．１部と、ポリオールとして、ポリオキシテトラメチレングリコール（分子量６５０、三菱化学（株）製）７０部と、ウレタン反応触媒として、ジブチルすずジラウレート０．０５部とを投入し、攪拌しながら、水素化キシリレンジイソシアネート２５部を滴下し、６５℃で２時間反応させて、ウレタンポリマー−アクリル系モノマー混合物を得た。なお、ポリイソシアネート成分とポリオール成分の使用量は、ＮＣＯ／ＯＨ（当量比）＝１．２５であった。その後、2−ヒドロキシエチルアクリレートを５部を添加した。
ウレタンポリマー−アクリル系モノマー混合物を、厚さ５０μｍの剥離処理したポリエチレンテレフタレートフィルム上に、硬化後の厚みが１００μｍになるように塗布し、凹凸面に剥離処理したポリエチレンフィルム（厚み７０μｍ）を重ねて被覆した後、高圧水銀ランプを用いて紫外線（照度１６３ｍＷ／ｃｍ２、光量２１００ｍＪ／ｃｍ２）を照射して硬化させて粘着シートを形成した。この後、被覆した凹凸剥離処理済みポリエチレンフィルムを剥離して、背面にエンボスが転写されたセパレータ付きの粘着シートを得た。
これをテープ貼付装置ＤＲ−３０００ＩＩ（日東精機製）を用いてＳｉウエハ表面に貼り合わせ、グラインダーＤＦＧ８５６０（Ｄｉｓｃｏ製）を用いて粘着シートで固定されたＳｉウエハの裏面をＳｉウエハの厚みが５０μｍになるよう研削した後、ウエハの装置搬送性、研削後ウエハ反り、水浸入について評価した。また作製した粘着シートの応力緩和率、段差追従性の経時変化、投錨力の測定を行った。 Example 1
In a reaction vessel equipped with a condenser, a thermometer, and a stirrer, 30 parts of tert-butyl acrylate, 20 parts of acrylic acid, 80 parts of isobornyl acrylate as an acrylic monomer, 2,2 as a photopolymerization initiator -Dimethoxy-1,2-diphenylethane-1-one (trade name “Irgacure 651”, manufactured by Ciba Specialty Chemicals Co., Ltd.) 0.1 part and polyol, polyoxytetramethylene glycol (molecular weight 650, Mitsubishi) 70 parts by Chemical Co., Ltd.) and 0.05 part of dibutyltin dilaurate as a urethane reaction catalyst were added, and 25 parts of hydrogenated xylylene diisocyanate was added dropwise with stirring and reacted at 65 ° C. for 2 hours. A urethane polymer-acrylic monomer mixture was obtained. In addition, the usage-amount of the polyisocyanate component and the polyol component was NCO / OH (equivalent ratio) = 1.25. Thereafter, 5 parts of 2-hydroxyethyl acrylate was added.
The urethane polymer-acrylic monomer mixture was applied onto a polyethylene terephthalate film having a thickness of 50 μm, and the thickness after curing was 100 μm. After coating, an adhesive sheet was formed by irradiating and curing ultraviolet rays (illuminance 163 mW / cm 2 , light amount 2100 mJ / cm 2 ) using a high-pressure mercury lamp. Thereafter, the coated polyethylene film with the uneven release treatment was peeled off to obtain a pressure-sensitive adhesive sheet with a separator having an emboss transferred on the back surface.
This was bonded to the Si wafer surface using a tape applicator DR-3000II (manufactured by Nitto Seiki), and the thickness of the Si wafer was fixed to 50 μm on the back surface of the Si wafer fixed with an adhesive sheet using a grinder DFG8560 (manufactured by Disco). After being ground, the wafer transportability, the wafer warpage after grinding, and water penetration were evaluated. Moreover, the stress relaxation rate of the produced adhesive sheet, the time-dependent change of level | step difference followability, and the anchoring force were measured.

比較例１
実施例１で凹凸セパレータで被覆したものを凹凸のない通常のＰＥＴセパレータ（３８μm）を用いた以外は実施例１と同様の方法で作製した。この粘着シートを用いて実施例１と同様の方法でウエハに貼り合わせ、評価を行った。 Comparative Example 1
It was produced in the same manner as in Example 1 except that the ordinary PET separator (38 μm) having no irregularities was used as the one coated with the irregular separator in Example 1. Using this adhesive sheet, it was bonded to a wafer in the same manner as in Example 1 and evaluated.

比較例２
アクリル酸ｎ−ブチル１００部、アクリル酸３部、２，２’−アゾビスイソブチロニトリル０．１部を２５℃の状態で、内容量５００ｍｌのフラスコに、全体が２００ｇとなるように配合して投入した。窒素ガスを約１時間フラスコに導入しながら攪拌し、内部の空気を窒素で置換した。その後、容器を加温して、内部温度を６０℃になるまで上昇させ、この状態で約６時間保持して重合を行い、ポリマー溶液を得た。
得られたポリマー溶液１００ｇに、ポリイソシアネート化合物（日本ポリウレタン工業社製：コロネートＬ）２ｇ、多官能エポキシ化合物（三菱瓦斯化学製：テトラッドＣ）０．５ｇを添加して、酢酸エチルで希釈し、均一になるまで攪拌して粘着剤溶液を得た。
得られた粘着剤溶液を、ＰＥＴセパレータ上に塗布し、乾燥オーブンにて７０℃及び１３０℃で、それぞれ３分間乾燥して、厚みが１５μｍの粘着剤層を形成し、基材であるEVA（エチレン-酢酸ビニル共重合体フィルム、１１５μｍ厚）に貼り合せて粘着シートを作製した。実施例１の粘着剤を乾燥後の厚みが３０μｍとなるように塗工した以外は実施例１と同様に、粘着シートを作製した。この粘着シートを用いて実施例１と同様の方法でウエハに貼り合わせ、評価を行った。 Comparative Example 2
Formulated with 100 parts of n-butyl acrylate, 3 parts of acrylic acid, and 0.1 part of 2,2′-azobisisobutyronitrile at 25 ° C. in a 500 ml flask with a total volume of 200 g. And put it in. The mixture was stirred while introducing nitrogen gas into the flask for about 1 hour, and the air inside was replaced with nitrogen. Thereafter, the container was heated, the internal temperature was raised to 60 ° C., and this state was maintained for about 6 hours for polymerization to obtain a polymer solution.
To 100 g of the obtained polymer solution, 2 g of a polyisocyanate compound (manufactured by Nippon Polyurethane Industry Co., Ltd .: Coronate L) and 0.5 g of a polyfunctional epoxy compound (manufactured by Mitsubishi Gas Chemical Co., Ltd .: Tetrad C) are added and diluted with ethyl acetate. Stir until homogeneous to obtain a pressure-sensitive adhesive solution.
The obtained pressure-sensitive adhesive solution was applied onto a PET separator and dried in a drying oven at 70 ° C. and 130 ° C. for 3 minutes to form a pressure-sensitive adhesive layer having a thickness of 15 μm. An adhesive sheet was prepared by adhering to an ethylene-vinyl acetate copolymer film (thickness: 115 μm). A pressure-sensitive adhesive sheet was prepared in the same manner as in Example 1 except that the pressure-sensitive adhesive of Example 1 was coated so that the thickness after drying was 30 μm. Using this adhesive sheet, it was bonded to a wafer in the same manner as in Example 1 and evaluated.

〔ウエハの装置搬送性〕
Ｄｉｓｃｏ製バックグラインダーＤＦＧ−８５６０にてＳｉウエハに貼り合わせた粘着シートの背面がロボットアームに貼り付くことなく搬送できるかを観察した。 [Wafer transferability]
It was observed whether the back surface of the adhesive sheet bonded to the Si wafer with a disco back grinder DFG-8560 could be conveyed without sticking to the robot arm.

〔研削後ウエハ反り〕
Ｄｉｓｃｏ製バックグラインダーＤＦＧ−８５６０にてＳｉウエハの厚みが５０μｍとなるまで研削し研削後のＳｉウエハの反り量は、研削１分後のＳｉウエハを粘着シートを貼り合わせた状態で平坦な場所に置き、端部の浮いている距離（ｍｍ）を測定することにより求めた。 [Wafer warpage after grinding]
The warpage of the Si wafer after grinding until the thickness of the Si wafer reaches 50 μm with Disco back grinder DFG-8560, the Si wafer after grinding for 1 minute is placed on a flat surface with the adhesive sheet attached. It was determined by placing and measuring the distance (mm) at which the end floated.

粘着シートの諸性質についての測定方法は以下の通りとした。
〔投錨力の測定方法〕
２０ｍｍ幅の粘着シートを２３℃においてバックグラインドテープ用剥離テープＢＴ−３１５（日東電工（株）製）と粘着面同士を貼り合せ、Ｔの字になるように速度３００ｍｍ／ｍｉｎで粘着面同士を剥がした時に投錨破壊するかを確認した。
〔応力緩和率〕
粘着シートを速度200ｍｍ/minで10％伸張させたて保持した時の初期の強度が1分後にどれくらい減少するかを確認した。
[テープ貼付1日後段差浮きと水浸漬評価]
Ｓｉミラーウエハに予め、１０ｍｍ幅、高さ３０μmのテープを貼付して段差を作製しておき、テープ貼付装置で段差と交差するようにテープを貼付したときの段差浮き幅を１日後の増加量で比較評価した。また、そのウエハを水に全面浸して、水が少しでも浸入した場合を「水浸入」、全く入らなかったものを「問題なし」とした。
実施例１及び比較例１〜２の結果を表１及び表２に示す。 Measurement methods for various properties of the pressure-sensitive adhesive sheet were as follows.
[Method of measuring anchoring force]
A 20 mm wide adhesive sheet is bonded at 23 ° C. to the back grind tape release tape BT-315 (manufactured by Nitto Denko Co., Ltd.) and the adhesive surfaces are bonded to each other at a speed of 300 mm / min. It was confirmed whether it would be thrown away when peeled off.
[Stress relaxation rate]
It was confirmed how much the initial strength when the pressure-sensitive adhesive sheet was stretched 10% at a speed of 200 mm / min and decreased after 1 minute.
[Step lift and water immersion evaluation one day after tape application]
A taper with a width of 10 mm and a height of 30 μm is applied in advance to a Si mirror wafer, and a step is created. When the tape is applied so as to cross the step with a tape application device, the step-floating width is increased by one day. It was compared and evaluated. In addition, when the wafer was completely immersed in water and water entered even a little, “water intrusion” was designated, and the case where no water entered at all was designated as “no problem”.
The results of Example 1 and Comparative Examples 1 and 2 are shown in Tables 1 and 2.

Figure 2012054431
Figure 2012054431

Figure 2012054431
Figure 2012054431

表１及び表２に示すとおり、基材及び粘着剤の界面が存在せず1層の粘着シートを用いた実施例１ではテープ貼付1日後の段差浮きが非常に小さく、水浸漬した場合もテープと段差の隙間から水が浸入することが無いため、テープ貼付後数日経ってからバックグラインドを行う場合も水浸入が起こらない。また、投錨力試験でも基材／粘着剤の界面が存在しない1層の粘着シートであるため、投錨破壊することがなく、ウエハからテープを剥離する際に粘着剤残り等の問題が発生しない。さらに背面をエンボス加工することでウエハ研削する際のロボット搬送でもアームにくっついてしまうことが無く、安定して搬送可能であり、極薄まで研削した場合にウエハに生じる反りを極限まで減らすことができる。   As shown in Tables 1 and 2, in Example 1 where the interface between the base material and the pressure-sensitive adhesive did not exist and a single-layer pressure-sensitive adhesive sheet was used, the level difference was very small one day after tape application, and the tape was also immersed in water. Since water does not enter through the gap between the step and the back grind after several days after the tape is applied, water infiltration does not occur. In addition, since it is a single-layer adhesive sheet that does not have a substrate / adhesive interface even in the anchoring force test, there is no anchorage failure and no problems such as adhesive residue remain when peeling the tape from the wafer. Furthermore, by embossing the back surface, robot transfer when grinding the wafer will not stick to the arm and can be carried stably, reducing the warpage that occurs on the wafer to the minimum when grinding to an extremely thin thickness. it can.

Claims (5)

半導体ウエハ表面に貼り合わせる半導体ウエハ用粘着シートであって、前記粘着シートは、基材層が存在せずアクリルウレタン樹脂により形成された１層からなることを特徴とする半導体ウエハ用粘着シート。   A pressure-sensitive adhesive sheet for a semiconductor wafer to be bonded to a surface of a semiconductor wafer, wherein the pressure-sensitive adhesive sheet is composed of one layer formed of an acrylic urethane resin without a base layer. 前記粘着シートは１０％伸張時の応力緩和率が４０％以上であることを特徴とする請求項１記載の半導体ウエハ用粘着シート。   The pressure-sensitive adhesive sheet for a semiconductor wafer according to claim 1, wherein the pressure-sensitive adhesive sheet has a stress relaxation rate of 40% or more when stretched by 10%. 前記粘着シートを３０μｍの段差に貼付した時の２４ｈ後のテープ浮き幅は初期と比較して４０％以内の増加率であることを特徴とする請求項１又は２記載の半導体ウエハ用粘着シート。   3. The pressure sensitive adhesive sheet for semiconductor wafer according to claim 1, wherein the tape floating width after 24 hours when the pressure sensitive adhesive sheet is stuck on a step of 30 [mu] m is an increase rate within 40% compared to the initial stage. 前記粘着シートの厚みが５μｍ〜１０００μｍであることを特徴とする請求項１〜３に記載の半導体ウエハ用粘着シート。   The thickness of the said adhesive sheet is 5 micrometers-1000 micrometers, The adhesive sheet for semiconductor wafers of Claims 1-3 characterized by the above-mentioned. 前記粘着シートの両面の粘着力が互いに異なる請求項１〜４記載の半導体ウエハ用粘着シート。   The pressure-sensitive adhesive sheet for semiconductor wafer according to claim 1, wherein the pressure-sensitive adhesive strength of both surfaces of the pressure-sensitive adhesive sheet is different from each other.
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